Synthesis of alkylboronic acids and alkylboronates

Related

Recent Literature

A mild Pd-catalyzed process for the borylation of primary alkyl bromides using
bis(pinacolato)diboron as a boron source tolerates a wide range of functional
groups on the alkyl bromide substrate and offers complete selectivity in the
presence of a secondary bromide. This approach has been extended to the use of
alkyl iodides and alkyl tosylates, as well as borylation reactions employing
bis(neopentyl glycolato)diboron as the boron source.
A. Joshi-Pangu, X. Ma, M. Diane, S. Iqbal, R. J. Kribs, R. Huang, C.-Y. Wang, M.
R. Biscoe, J. Org. Chem., 2012,
77, 6629-6633.

Hydroboration of terminal and internal aliphatic alkenes with
pinacolborane was carried out at room temperature in the presence of dppm and [Ir(cod)Cl]2 resulting in addition of the boron atom to the terminal carbon with a selectivity of more than
99%. A complex
prepared from dppe and [Ir(cod)Cl]2 resulted in the best yields for
vinylarenes.
Y. Yamamoto, R. Fujikawa, T. Umemoto, N. Miyaura, Tetrahedron,
2004,
60, 10695-10700.

A simple protocol for the borylation of alkenes with use of impregnated copper
on magnetite showed a very broad scope. All type of olefins could be used with
similar results. The catalyst can be magnetically removed and reused several
times, showing similar activity.
R. Cano, D. J. Ramón, M. Yus, J. Org. Chem., 2010,
75, 3458-3460.

(E)- and (Z)-silyl and aryl-subsituted homoallylic
methanesulfonates were converted to the corresponding cis- and trans-1-silyl-2-borylcyclobutanes
as well as 1-phenyl-2-borylcyclobutanes in the presence of a CuCl/dppp catalyst,
bis(pinacolato)diboron, and K(O-t-Bu)in THF. Stereospecific
derivatizations of the cis- and trans-borylcyclobutanes were
carried out to demonstrate the utility of the borylcyclobutanes.
H. Ito, T. Toyoda, M. Sawamura, J. Am. Chem. Soc., 2010,
132, 5990-5992.

Using bis(pinacolato)diboron, catalytic amounts of CuII, and various
amine bases in water under atmospheric conditions at rt, acyclic and cyclic
α,β-unsaturated ketones and esters are β-borylated in good yield. Mechanistic
investigations suggest that the role of the amine is not only to coordinate to
CuII but also to activate a nucleophilic water molecule to form a
reactive sp2-sp3 diboron complex.
S. B. Thorpe, J. A. Calderone, W. L. Santos, Org. Lett., 2012,
14, 1918-1921.

A simple protocol for the borylation of alkenes with use of impregnated copper
on magnetite showed a very broad scope. All type of olefins could be used with
similar results. The catalyst can be magnetically removed and reused several
times, showing similar activity
R. Cano, D. J. Ramón, M. Yus, J. Org. Chem., 2010,
75, 3458-3460.

(η6-mes)IrBpin3 or [Ir(COD)OMe]2 catalyzes the
borylation of cyclopropanes in the presence of the phenanthroline derivative
2,9-Me2phenanthroline as ligand. The borylation occurs selectively at
the methylene C-H bonds of the cyclopropane ring in high diasteroselectivities.
The cyclopropylboronate esters can be converted to trifluoroborate salts,
boronic acids, cyclopropylarenes, cyclopropylamines, and cyclopropanols.
C. W. Liskey, J. F. Hartwig, J. Am. Chem. Soc., 2013,
135, 3375-3378.